JP2006293320A - Method for producing toner, toner, and apparatus for producing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a toner which ensures no or very small range of variation due to particles in various property values required for a toner and is used in a developer for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing or the like, a toner produced by the method and an apparatus for producing a toner using the method. <P>SOLUTION: The method for producing the toner includes ejecting a toner composition fluid containing a toner composition which contains at least a resin and a colorant, from a nozzle vibrated at a constant frequency to make the toner composition fluid into droplets, and solidifying the droplets to be made into particles. Alternatively, the method for producing the toner includes ejecting a solution or dispersion of a material for a toner containing at least a resin and a colorant, from a nozzle vibrated at a constant frequency to make the solution or dispersion into droplets, and drying the droplets. The method preferably uses a vibration producing means to vibrate the nozzle. It is preferable that the vibration producing means and the nozzle get contact with each other and the nozzle is directly vibrated by the vibration producing means. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a toner used as a developer for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, etc., a toner produced thereby, and the toner production method. The present invention relates to the toner manufacturing apparatus used.

  Developers used in electrophotography, electrostatic recording, electrostatic printing, and the like are temporarily attached to an image carrier such as an electrostatic latent image carrier on which an electrostatic charge image is formed in the development process. Then, after being transferred from the electrostatic latent image carrier to a transfer medium such as transfer paper in the transfer step, it is fixed on the paper surface in the fixing step. At that time, as a developer for developing an electrostatic charge image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner, and a one-component developer not requiring a carrier (magnetic toner, Non-magnetic toners are known.

  Conventional dry toners used for electrophotography, electrostatic recording, electrostatic printing, and the like are those obtained by melt-kneading a toner binder such as a styrene resin and a polyester resin together with a colorant and finely pulverizing them, so-called pulverized toner. Is widely used.

  Recently, a toner production method using a suspension polymerization method or an emulsion polymerization aggregation method, so-called polymerization type toner, has been studied. In addition to this, a method called volumetric shrinkage called a polymer dissolution suspension method has been studied (see Patent Document 1). In this method, a toner material is dispersed and dissolved in a volatile solvent such as a low-boiling organic solvent, and this is emulsified and formed into droplets in an aqueous medium containing a dispersant, and then the volatile solvent is removed. Unlike the suspension polymerization method and emulsion polymerization aggregation method, this method is a versatile resin that can be used, and in particular, a polyester resin useful for a full color process that requires transparency and smoothness of the image area after fixing. It is excellent in that it can be used.

  However, since the above-described polymerization type toner is premised on the use of a dispersant in an aqueous medium, a dispersant that impairs the charging characteristics of the toner remains on the toner surface and the environmental stability is impaired. It is known that a defect occurs or a very large amount of washing water is required to remove this, and it is not always satisfactory as a manufacturing method.

  As an alternative method for producing toner, a method has been proposed in which fine droplets are formed using a piezoelectric pulse and then dried and solidified to form a toner (see Patent Document 2). Furthermore, a method has also been proposed in which fine droplets are formed by utilizing thermal expansion in the nozzle, and this is dried and solidified to form a toner (see Patent Document 3). Furthermore, a method for performing the same processing using an acoustic lens has been proposed (see Patent Document 4). However, in these methods, the number of droplets that can be ejected from one nozzle per unit time is small, and there is a problem that productivity is low, and at the same time, the spread of particle size distribution due to coalescence of droplets is unavoidable, Also in terms of monodispersity, it was not satisfactory.

JP-A-7-152202 JP 2003-262976 A JP 2003-280236 A Japanese Patent Laid-Open No. 2003-262977

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention can efficiently produce a toner, and further has a single particle dispersibility with a particle size that has never been obtained so that many characteristic values required for the toner such as fluidity and charging characteristics are obtained. In developing agents for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc., which have no or very little variation due to particles as seen in conventional manufacturing methods. It is an object of the present invention to provide a toner production method to be used, a toner produced thereby, and a toner production apparatus using the toner production method.

Means for solving the problems are as follows. That is,
<1> A toner composition fluid containing a toner composition containing at least a resin and a colorant is ejected from a nozzle oscillated at a constant frequency to form droplets, which are solidified into particles. A toner manufacturing method characterized by the above.
<2> A solution or dispersion of a toner material containing at least a resin and a colorant is discharged from a nozzle oscillated at a constant frequency to form droplets, and the droplets are dried. This is a toner manufacturing method.
In the toner production method according to <1> and <2>, when the toner composition fluid, the dissolved or dispersed liquid is vibrated at a constant frequency, the nozzles are constricted at a constant interval when ejected from the nozzle. It is possible to produce a true spherical toner having a monodispersed particle size distribution by dividing a certain amount of droplets. Therefore, it is excellent in uniformity of powder characteristics represented by charge amount distribution, fluidity, and the like, and an image extremely faithful to the latent image can be obtained. Further, since mechanical stress is remarkably reduced from the uniformity of the toner shape, the life of the toner is dramatically increased, and an image with excellent image quality can be obtained for a long period of time.
<3> The toner production method according to any one of <1> to <2>, further including vibration generation means for vibrating the nozzle.
<4> The toner production method according to <3>, wherein the vibration generating unit and the nozzle are in contact with each other, and the nozzle is directly vibrated by the vibration generating unit.
<5> The toner manufacturing method according to any one of <3> to <4>, wherein the vibration vibration generating unit is a piezoelectric body and vibrates at a constant frequency by expansion and contraction of the piezoelectric body.
In the toner production method according to <5>, by constricting the liquid injection at constant intervals in the liquid column ejected from the nozzle by constant vibration, the liquid injection tip portion breaks up into a constant amount of droplets, Solid particles having a constant particle size can be continuously produced.
<6> The toner production method according to any one of <1> to <5>, wherein the discharge hole of the nozzle is formed of a metal plate having a thickness of 5 to 50 μm, and an opening diameter thereof is 3 to 5 μm. .
<7> The method for producing a toner according to any one of <1> to <6>, wherein a droplet discharged from a nozzle is given a positive charge or a negative charge by induction charge.
In the method for producing a toner according to <7>, the droplets discharged from the nozzle are given a positive charge or a negative charge by inductive charging, so that the droplets caused by electrostatic repulsion or solidified particles are coalesced. Can be obtained, and particles having an extremely monodispersed particle size distribution can be obtained.
<8> The toner production method according to <7>, wherein the induction charge is performed by passing a droplet discharged from a nozzle between a pair of electrodes to which a DC voltage is applied.
<9> Any one of <2> to <8> above, wherein the ionic conductivity of the solution or dispersion of the toner material containing at least a resin and a colorant is 1.0 × 10 ⁻⁷ S / m or more. The toner production method as described in 1. above.
<10> From the above <2> to <9>, the electrolytic conductivity as a solvent of a solution or dispersion of a toner material containing at least a resin and a colorant is 1.0 × 10 ⁻⁷ S / m or more. The toner production method according to any one of the above.
<11> An air flow is generated by flowing a dry gas in the same direction as the droplet discharge direction, and the air stream causes the droplets to be transported in a solvent removal facility, and the solvent in the droplets is removed during the transport. The toner manufacturing method according to any one of <1> to <10>, wherein the toner particles are formed by forming the toner particles.
In the toner manufacturing method according to <11>, the air is generated by flowing a dry gas in the same direction as the droplet discharge direction, and the droplet is transported in the solvent removal facility by the air flow. A mechanism can also be eliminated, and application to new development methods is also possible.
<12> The toner production method according to <11>, wherein the dry gas is either air or nitrogen gas.
<13> The toner production method according to any one of <11> to <12>, wherein the temperature of the dry gas is 40 to 200 ° C.
<14> The solvent removal equipment has a transport path whose periphery is covered with an electrostatic curtain charged in the opposite polarity to the charge of the droplet, and the droplet <1> is allowed to pass through the transport path. > To <13>.
<15> A toner manufactured by the toner manufacturing method according to any one of <1> to <14>.
<16> The toner according to <15>, wherein the particle size distribution (mass average particle size / number average particle size) is in the range of 1.00 to 1.05.
<17> The toner according to <16>, wherein the mass average particle diameter is 1 to 20 μm.
<18> A droplet forming means for forming a droplet by discharging a solution or dispersion of a toner material containing at least a resin and a colorant from a nozzle oscillated at a constant frequency; And a toner particle forming unit that forms toner particles by drying the droplets by removing the solvent contained in the toner.
<19> The toner manufacturing apparatus according to <18>, wherein the droplet forming unit includes a vibration generating unit that directly vibrates the nozzle.
<20> The toner manufacturing apparatus according to <19>, wherein the vibration generating unit vibrates the nozzle simultaneously with the passage of the dissolved or dispersed liquid.
<21> The solution according to any one of <18> to <20>, further comprising a storage unit that stores a solution or dispersion of the toner material and supplies the solution or dispersion of the toner material to the droplet forming unit. This is a toner manufacturing apparatus.
<22> Any one of <18> to <21>, wherein the nozzle is vibrated at a constant frequency by expansion and contraction of the piezoelectric body, and the number of ejection holes of the nozzle vibrated by one piezoelectric body is 1 to 300 The toner manufacturing apparatus described in the above.
<23> The toner production apparatus according to any one of <18> to <22>, wherein the toner production apparatus includes a plurality of nozzles, and the droplets ejected from each nozzle are dried by one solvent removal facility.
<24> The toner production apparatus according to any one of <18> to <23>, wherein the constant frequency is 50 kHz to 50 MHz.
<25> The toner manufacturing apparatus according to any one of <18> to <24>, wherein the constant frequency is 100 kHz to 10 MHz.
<26> The toner particles formed by allowing the droplets to pass through the conveyance path are temporarily neutralized by a static eliminator, and then the toner particles are accommodated in the toner collecting unit <18>. To <25>.
<27> The toner production apparatus according to <26>, wherein the charge removal by the charge remover is performed by soft X-ray irradiation.
<28> The toner production apparatus according to <26>, wherein the charge removal by the charge remover is performed by plasma irradiation.
<29> The toner collecting portion for collecting the toner particles has a tapered surface whose opening diameter is gradually reduced, and the toner particles are dried from the outlet portion where the opening diameter is reduced from the inlet portion by using dry gas. The toner manufacturing apparatus according to any one of <18> to <28>, wherein the dry gas flow is formed and the toner particles are transferred to the toner storage container by the dry gas flow.
<30> The toner production apparatus according to <29>, wherein the flow of the dry gas is a vortex.
<31> The toner production apparatus according to any one of <18> to <30>, wherein the toner collection unit and the toner storage container are formed of a conductive material and are grounded.
<32> The toner production apparatus according to any one of <18> to <31>, which is an exposure protection specification.

According to the present invention, the conventional problems can be solved, the toner can be produced efficiently, and the particles having a monodispersibility with an unprecedented particle size can be used. In many of the characteristic values required for the above, there is no or very little variation in the particle size observed in conventional manufacturing methods, and electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. It is possible to provide a method for producing a toner used as a developer for developing, a toner produced thereby, and a toner production apparatus using the toner production method.
Specifically, there are no fluctuations due to particle variations seen in the conventional production methods for pulverized toners and chemical toners, or even extremely small fluctuations that can be almost ignored. Has characteristics. The realization of these characteristics can be said to be a characteristic that can be obtained only by the present invention. However, the realization of this characteristic makes it possible to form an image almost faithful to the latent image formed on the photosensitive member. In addition, the same feature makes it possible to maintain the effect over a long period of time. In other words, by achieving uniformity in particle size distribution, uniformity in shape, and uniformity in surface condition, the mechanical stress required to reach the toner charge amount set in the electrophotographic process is extremely small and wasteful. This is presumably due to a dramatic increase in toner life. This makes it possible to obtain an image with excellent image quality over a long period of time.

(Toner production method)
In the toner production method of the present invention, a toner composition fluid containing a toner composition containing at least a resin and a colorant is discharged from a nozzle oscillated at a constant frequency to form droplets, and the droplets are solidified. In other words, a toner material containing at least a resin and a colorant is discharged or discharged from a nozzle oscillated at a constant frequency to form droplets, and the droplets are dried. It is characterized by making it.

-Device-
An apparatus used in the toner manufacturing method of the present invention (hereinafter also referred to as “toner manufacturing apparatus”) is not particularly limited as long as it is an apparatus capable of manufacturing toner by the manufacturing method, and is appropriately selected. A droplet forming means that forms a droplet by discharging a solution or dispersion of a toner material containing at least a resin and a colorant from a nozzle that is vibrated at a constant frequency, which can be used; It is preferable to use a toner manufacturing apparatus having toner particle forming means for drying the droplets by removing the solvent contained in the droplets to form toner particles. In the toner manufacturing apparatus, it is more preferable that the droplet forming unit includes a vibration generating unit that directly vibrates the nozzle, and the vibration generating unit vibrates the nozzle simultaneously with the passage of the dissolved or dispersed liquid. It is more preferable to have a storage means for storing the toner material dissolved or dispersed liquid and supplying the toner material dissolved or dispersed liquid to the droplet forming means.
As the preferred toner manufacturing apparatus, for example, as shown in FIG. 1, at least a slurry reservoir 15 as the storage unit, and a nozzle 1 as the droplet forming unit provided in the drying container 10 , The electrode 2, the solvent removal equipment 3 as the toner particle forming means, the static eliminator 4, and the toner collecting portion 12, and as shown in FIG. 2, the piezoelectric as the vibration generating means. A device having the body 21 is preferably exemplified.
In the toner manufacturing apparatus shown in FIG. 1, the dissolved or dispersed liquid stored in the slurry reservoir 15 is supplied to the nozzle 1 through the liquid transport tube 9 by appropriately adjusting the supply amount by the metering pump 14. After being discharged as a droplet 11 from the nozzle 1, the droplet 11 is charged by the electrode 2, and then the solvent is removed by the solvent removal equipment 3 to form toner particles 6. The toner particles 6 are then discharged by the static eliminator 4. After the charge removal, the toner is collected in the toner collecting unit 5 by the vortex 7 and conveyed to the toner reservoir 12.
Hereinafter, the toner manufacturing apparatus will be described in detail for each member.

--Nozzle and piezoelectric body--
As described above, the nozzle 1 is a member that discharges a solution or dispersion of a toner material into droplets.
There is no restriction | limiting in particular as a material and shape of the said nozzle, Although it can be set as the shape selected suitably, For example, an ejection hole is formed with a metal plate with a thickness of 5-50 micrometers, and the opening diameter is 3-3. A thickness of 35 μm is preferable from the viewpoint of generating micro droplets having a very uniform particle diameter by applying a vibration to the nozzle 1 itself when a solution is ejected from the nozzle 1 to thereby impart a shearing force. The aperture diameter means a diameter if it is a perfect circle, and a minor diameter if it is an ellipse.
The means for applying vibration to the nozzle 1 is not particularly limited as long as it can provide reliable vibration at a constant frequency, and can be appropriately selected and used. From the above viewpoint, for example, As shown in FIG. 2, the nozzle 1 is preferably vibrated at a constant frequency by the expansion and contraction of the piezoelectric body 21.
The piezoelectric body 21 has a function of converting electrical energy into mechanical energy. Specifically, it is expanded and contracted by applying a voltage, and the nozzle can be vibrated by the expansion and contraction.
Examples of the piezoelectric body include piezoelectric ceramics such as lead zirconate titanate (PZT). However, since the amount of displacement is generally small, the piezoelectric body is often used by being laminated. In addition, piezoelectric polymers such as polyvinylidene fluoride (PVDF), single crystals such as quartz, LiNbO ₃ , LiTaO ₃ , KNbO ₃ , and the like can be given.
The constant frequency is not particularly limited and may be appropriately selected according to the purpose. However, 50 kHz to 50 MHz is preferable, and 100 kHz to 10 MHz is preferable from the viewpoint of generating minute droplets having a very uniform particle diameter. More preferably, 100 kHz to 450 kHz is particularly preferable.
Although only one nozzle 1 may be provided, from the viewpoint of generating minute droplets having a very uniform particle diameter, a plurality of nozzles 1 are provided, and the droplets 6 ejected from each nozzle are provided with one solvent removal facility. In the illustrated example, it is preferable that the solvent is removed by the solvent removal equipment 3.
From the same point of view, it is preferable that the piezoelectric body 21 also vibrates the discharge hole with one piezoelectric body.

  Here, as shown in FIG. 2, it is preferable that the piezoelectric body 21 and the nozzle 1 have a structure in which at least a part thereof is in contact and the vibration due to expansion and contraction of the piezoelectric body directly vibrates the nozzle. With this method, even when droplets are simultaneously ejected from a plurality of nozzles provided on one metal plate by vibration of one piezoelectric body, the vibration of the piezoelectric body is filled in another medium, for example, a liquid chamber. Compared with the case where vibration is applied through the formed liquid, it is possible to discharge more monodispersed droplets. This is presumably because when the vibration is applied to the nozzle through the liquid, the speed at which the vibration is transmitted to the nozzle varies depending on the distance from the piezoelectric body. For this reason, when a plurality of nozzles are provided, a time lag occurs in the droplets ejected from each nozzle, and the ejection amount differs between the nozzles. Even in the method of applying vibration through the liquid in the liquid chamber, if the droplets are ejected from one nozzle by the vibration of one piezoelectric body, the variation among nozzles can be suppressed considerably, but ejection from a large number of nozzles is considered in consideration of productivity. In order to perform this, it is not preferable because the number of piezoelectric bodies is the same as that of the nozzles.

  2, the reference numeral 16 denotes an insulating substrate, 17 denotes a liquid supply flow path, 18 denotes a DC high-voltage power source, 19 denotes an O-ring, 20 denotes dispersed air, and the piezoelectric body 21 expands and contracts to contact the nozzle 1. As a result, the dissolved or dispersed liquid supplied through the liquid supply flow path 17 provided across the nozzle 1 and the O-ring 19 is used as the droplet 11, and the DC voltage is supplied from the DC high-voltage power supply 18 by the dispersion air 20. Is fed to the electrode 2 to which is applied. The DC voltage is not applied to any part other than the electrode 2 by the insulating substrate 16.

  The number of ejection holes of the nozzle vibrated by the one piezoelectric body is not particularly limited, but is 1 to 300 in order to more surely generate micro droplets having a very uniform particle diameter. preferable. Therefore, the number of the nozzles 1 is preferably 1 to 15, and the number of ejection holes of the nozzle 1 is preferably 1 to 20 per nozzle.

--- Electrode--
The electrode 2 is a member for charging the droplet 6 discharged from the nozzle into monodisperse particles.
The electrode 2 is a pair of members disposed facing the nozzle 1, and the shape thereof is not particularly limited and can be appropriately selected. For example, as shown in FIG. Preferably formed.
The charging method using the electrode 2 (hereinafter also referred to as “ring electrode”) is not particularly limited, but a constant charge amount can always be given to the droplet 11 discharged from the nozzle. Therefore, for example, it is preferable to give a positive charge or a negative charge to the droplet 11 by induction charge. More specifically, the dielectric charging is preferably performed by passing the droplet through a ring electrode to which a DC voltage is applied.
Further, as the method of inductive charging, it is possible to charge a droplet by directly applying a DC voltage to the nozzle and providing a potential difference with the ground arranged at the bottom of the drying equipment. In this case, a potential can be applied through the conductive toner solution or dispersion in the slurry reservoir 15. If the liquid supply to the slurry reservoir 15 is insulated by using air pressure or the like, induction charging can be achieved relatively easily.
It has already been proved that droplets in an air stream are in a highly charged state by electrospray method or fine particle production by electrostatic spraying. In this case, it is possible in principle to maintain a charge amount higher than the charge to the solid from the effect of reducing the surface area of the droplet by evaporation of the volatile component, and more highly charged solid particles can be obtained.

--Solvent removal equipment--
The solvent removal equipment 3 is not particularly limited as long as the solvent of the droplets 11 can be removed, but an air flow is generated by flowing a dry gas in the same direction as the droplet 6 discharge direction. It is preferable to form the toner particles 6 by transporting the droplet 6 in the solvent removal equipment 3 and removing the solvent in the droplet 11 during the transport. Here, “dry gas” means a gas having a dew point temperature of −10 ° C. or lower under atmospheric pressure.
The dry gas is not particularly limited as long as it is a gas that can dry the droplets 11, and examples thereof include air and nitrogen gas.
Although there is no restriction | limiting in particular as a method of flowing the said dry gas to the solvent removal equipment 3, For example, the method of flowing from the dry gas supply tube 13 as shown in FIG.
The temperature of the drying gas is preferably higher in terms of drying efficiency, and even if a drying gas having a boiling point higher than the solvent used is used due to the characteristics of spray drying, the constant rate drying region during drying is used. Thus, the droplet temperature does not rise above the boiling point of the solvent, and the resulting toner is not thermally damaged. However, since the main constituent material of the toner is a thermoplastic resin, when it is exposed to a dry gas that is higher than the boiling point of the resin to be used after drying, that is, in the rate-decreasing drying region, the toner is liable to be thermally fused. There is a risk that the monodispersibility may be impaired. Therefore, specifically, the temperature of the dry gas is preferably, for example, 40 to 200 ° C, more preferably 60 to 150 ° C, and particularly preferably 75 to 85 ° C.
In addition, as shown in FIG. 1, from the viewpoint of preventing the droplet 11 from adhering to the inner wall surface of the solvent removal equipment 3 from the wall surface of the solvent removal equipment 3, the polarity is opposite to the charge of the droplets. It is preferable that a charged electric field curtain 8 is provided, a transport path whose periphery is covered with the electric field curtain is formed, and liquid droplets are allowed to pass through the transport path.

--- Static eliminator--
The static eliminator 4 temporarily neutralizes the charge of the toner particles 7 formed by allowing the droplets 11 to pass through the conveyance path, and then accommodates the toner particles 6 in the toner collecting unit 5. It is a member for.
There is no particular limitation on the method of static elimination by the static eliminator 4, and a conventionally known method can be appropriately selected and used. However, since neutralization can be performed efficiently, for example, soft X-rays can be used. Preferably, the irradiation is performed by irradiation, plasma irradiation, or the like.

-Toner collection part-
The toner collecting unit 5 is a member provided at the bottom of the toner manufacturing apparatus from the viewpoint of efficiently collecting and transporting toner.
The structure of the toner collecting portion 5 is not particularly limited as long as the toner can be collected and can be appropriately selected. From the above viewpoint, a tapered surface whose opening diameter is gradually reduced is provided as in the illustrated example. The toner particles 6 are formed from the outlet portion whose opening diameter is smaller than the inlet portion, using the dry gas to form the flow of the dry gas, and the toner particles are transferred to the toner storage container by the flow of the dry gas. It is preferable to transfer it.
As the transfer method, the toner particles 6 may be pumped to the toner storage container 12 by the dry gas as shown in the example, or the toner particles 6 may be sucked from the toner storage container 12 side.
Although there is no restriction | limiting in particular as a flow of the said dry gas, From a viewpoint which can generate the centrifugal force and can reliably transfer the toner particle 6, it is preferable that it is a vortex | eddy_current.
Further, from the viewpoint of more efficiently transporting the toner particles 6, it is more preferable that the toner collecting unit 5 and the toner storage container 12 are formed of a conductive material and are connected to the ground. preferable. The toner manufacturing apparatus preferably has an exposure specification.

--- Droplet--
As described above, the droplet 6 is generated by discharging a solution or dispersion of a toner material containing a specific substance from the nozzle 1 oscillated at a constant frequency. The toner material will be described in a separate “toner” section.
The solution or dispersion liquid for the toner material is not particularly limited as long as the toner material is at least one of dissolved and dispersed, and can be appropriately selected and used. From the viewpoint of maintaining it, the electrolytic conductivity is preferably 1.0 × 10 ⁻⁷ S / m or more.
From the same viewpoint, the electrolytic conductivity as a solvent of the dissolved or dispersed liquid is preferably 1.0 × 10 ⁻⁷ S / m or more.
The method for dissolving or dispersing the toner material is not particularly limited, and a commonly used method can be appropriately selected. Specifically, a toner binder such as a styrene acrylic resin, a polyester resin, a polyol resin, and an epoxy resin may be melt-kneaded with a colorant or the like and finely pulverized, or obtained during the production. The kneaded product may be once dissolved in an organic solvent in which the resin component is soluble and then processed as fine droplets.

-Action-
According to the toner manufacturing method of the present invention described in detail above, the number of droplets generated from one discharge hole of the nozzle is very large, tens of thousands to several million per second, and the discharge holes are further increased. It is also easy to increase. Further, from the viewpoint of obtaining a very uniform droplet diameter and sufficient productivity, it can be said to be the most suitable method for producing toner. Furthermore, in this production method, the particle diameter of the toner finally obtained can be accurately determined by the following calculation formula (1), and there is almost no change in the particle diameter depending on the material used.
〔a formula〕
Dp = (6QC / πf) ^(1/3) (1)
Where Dp: solid particle diameter, Q: liquid flow rate (determined by pump flow rate and nozzle diameter), f: vibration frequency, and C: volume concentration of solid content.
The toner particle diameter can be accurately calculated only by the above formula (1), but more simply can be obtained by the following formula (2).
〔a formula〕
Solid content volume concentration (volume%) = (solid particle diameter / droplet diameter) ³ (2)
That is, the diameter of the toner particles obtained by the present invention is twice the nozzle opening diameter regardless of the vibration frequency at which the droplets are ejected. Therefore, the target solid particle diameter can be obtained by obtaining and adjusting the solid content concentration in advance from the relationship of the above formula (2). For example, when the nozzle diameter is 7.5 μm, the droplet diameter is 15 μm. Therefore, if the solid content volume concentration is 6.40% by volume, 6.0 μm solid particles can be obtained. In this case, the vibration frequency is preferably higher from the viewpoint of productivity, but Q (liquid flow rate) is determined from the calculation formula (1) in accordance with the vibration frequency determined here.
In the conventional manufacturing methods, the particle size often varies greatly depending on the material used, but in this manufacturing method, the particle size as set is controlled by managing the droplet diameter and solid content concentration when discharging. It becomes possible to continuously obtain particles having a diameter.

  Further, since the toner obtained by the present invention has a very uniform particle size, the fluidity in the toner base is very high. Therefore, even when an external additive is added for the purpose of reducing the adhesive force to a manufacturing apparatus or the like, the effect can be exhibited in an extremely small amount. Considering the deterioration of external additives due to stress and the safety of fine particles to the human body, it is preferable not to use such external additives as much as possible, which is also an advantage of the present invention.

(toner)
The toner of the present invention is a toner manufactured by the above-described toner manufacturing method of the present invention.
As the toner, a toner having a monodispersed particle size distribution can be obtained by the toner manufacturing method.
Specifically, the particle size distribution (mass average particle diameter / number average particle diameter) of the toner is preferably in the range of 1.00 to 1.05. Moreover, as a mass mean particle diameter, it is preferable that it is 1-20 micrometers.
The toner obtained by the toner manufacturing method can be easily redispersed, that is, floated in an air current due to the electrostatic repulsion effect. For this reason, the toner can be transported to the development area without using a transport means such as that used in the conventional electrophotographic system. That is, even a weak air current has sufficient transportability, and the toner can be transported to the development area with a simple air pump and developed as it is. Development is so-called power cloud development, and since there is no disturbance in image formation due to airflow, extremely good electrostatic latent image development can be performed. Further, the toner of the present invention can be applied without any problem even if it is a conventional developing system. At this time, members such as a carrier and a developing sleeve are merely used as a toner conveying unit, and there is no need to consider a frictional charging mechanism that has been conventionally shared in function. Therefore, since the degree of freedom of the material is greatly increased, the durability can be greatly improved, an inexpensive material can be used, and the cost can be reduced.
The toner material that can be used in the present invention can be the same as the conventional electrophotographic toner. That is, a toner binder such as a styrene acrylic resin, a polyester resin, a polyol resin, and an epoxy resin is dissolved in various organic solvents, a colorant is dispersed, and a release agent is dispersed or dissolved. Desired toner particles can be produced by drying and solidifying into fine droplets by a toner production method. It is also possible to obtain a target toner by drying and solidifying a liquid obtained by dissolving or dispersing a kneaded material obtained by hot-melt kneading the above materials in various solvents once into fine droplets by the toner production method. is there.

-Toner material-
The toner material contains at least a resin and a colorant and, if necessary, other components such as a carrier and wax.

--Resin--
Examples of the resin include at least a binder resin.
The binder resin is not particularly limited, and a commonly used resin can be appropriately selected and used. For example, a styrene monomer, an acrylic monomer, a methacrylic monomer, etc. Vinyl polymers, copolymers of these monomers or two or more types, polyester polymers, polyol resins, phenol resins, silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, terpene resins , Coumarone indene resin, polycarbonate resin, petroleum resin, and the like.
Examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, and pn-. Amyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene , Styrene such as p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, or derivatives thereof.
Examples of the acrylic monomer include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, and acrylic. Examples include 2-ethylhexyl acid, stearyl acrylate, 2-chloroethyl acrylate, acrylic acid such as phenyl acrylate, or esters thereof.
Examples of the methacrylic monomer include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, and methacrylic acid. And methacrylic acid or esters thereof such as 2-ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.
The following (1)-(18) is mentioned as an example of the other monomer which forms the said vinyl polymer or a copolymer. (1) Monoolefins such as ethylene, propylene, butylene and isobutylene; (2) Polyenes such as butadiene and isoprene; (3) Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; (4) Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; (5) Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; (6) Vinyl methyl ketone, vinyl hexyl ketone and methyl. Vinyl ketones such as isopropenyl ketone; (7) N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone; (8), vinyl naphthalenes; (9) acrylonitrile, Such as methacrylonitrile, acrylamide, etc. (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; (11) maleic anhydride, citraconic anhydride, Unsaturated dibasic acid anhydrides such as itaconic anhydride and alkenyl succinic anhydride; (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester Monoesters of unsaturated dibasic acids such as citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester; (13) dimethylmaleic acid, dimethylfumaric acid, etc. (14) α, β-unsaturated acids such as crotonic acid and cinnamic acid; (15) α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride; 16) Monomers having a carboxyl group such as anhydrides of the α, β-unsaturated acids and lower fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof; ) Acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; (18) 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1 Monomers having a hydroxy group such as hydroxy-1-methylhexyl) styrene.
In the toner of the present invention, the vinyl polymer or copolymer of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the crosslinking agent used in this case include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene. Examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, and 1,6. Examples include xanthdiol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylates of these compounds with methacrylate. Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, and dipropylene. Examples include glycol diacrylate and those obtained by replacing acrylate of these compounds with methacrylate.

  Other examples include diacrylate compounds and dimethacrylate compounds linked by a chain containing an aromatic group and an ether bond. Examples of polyester diacrylates include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.).

  Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds in place of methacrylate, triallyl cyanide. Examples include nurate and triallyl trimellitate.

  These cross-linking agents are preferably used in an amount of 0.01 to 10 parts by mass, and 0.03 to 5 parts by mass, with respect to 100 parts by mass of the other monomers forming the vinyl polymer or copolymer. More preferred. Among these cross-linking agents, aromatic divinyl compounds (particularly divinylbenzene), diacrylate compounds connected by a bond chain containing one aromatic group and an ether bond from the viewpoint of fixing properties and offset resistance to toner resins. Are preferred. Among these, a combination of monomers that becomes a styrene copolymer or a styrene-acrylic copolymer is preferable.

  Examples of the polymerization initiator used in the production of the vinyl polymer or copolymer of the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1 , 1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2 ′ , 4'-dimethyl-4'-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexanone Ketone peroxides such as oxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di -Tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, di-isopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate Di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexyl Sulfonyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexarate, tert-butyl peroxylaurate, tert-butyl-oxybenzoate, tert- Butyl peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, isoamyl peroxy-2-ethylhexanoate, di-tert-butyl Kisa Hydro terephthalate to Rupaokishi, tert- butylperoxy azelate, and the like.

When the binder resin is a styrene-acrylic resin, it is at least 1 in the region of a molecular weight of 3,000 to 50,000 (in terms of number average molecular weight) in terms of molecular weight distribution by GPC of a component soluble in tetrahydrofuran (THF) as a resin component. A resin in which one peak is present and at least one peak is present in a region having a molecular weight of 100,000 or more is preferable in terms of fixing property, offset property and storage property. Further, as the THF soluble component, a binder resin in which a component having a molecular weight distribution of 100,000 or less is 50 to 90% is preferable, and a binder resin having a main peak in a region having a molecular weight of 5,000 to 30,000. Is more preferable, and a binder resin having a main peak in the region of 5,000 to 20,000 is most preferable.
The acid value when the binder resin is a vinyl polymer such as styrene-acrylic resin is preferably 0.1 mgKOH / g to 100 mgKOH / g, and preferably 0.1 mgKOH / g to 70 mgKOH / g. Is more preferable, and most preferably 0.1 mgKOH / g to 50 mgKOH / g.

The following are mentioned as a monomer which comprises the said polyester-type polymer.
Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or diol obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide to bisphenol A, etc. Is mentioned.
In order to crosslink the polyester resin, it is preferable to use a trivalent or higher alcohol together.
Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, such as dipentaerythritol, tripentaerythritol, 1,2,4- Butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene , Etc.

  Examples of the acid component that forms the polyester polymer include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, and alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid. Or its anhydride, maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid and other unsaturated dibasic acids, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride And unsaturated dibasic acid anhydrides. Examples of the trivalent or higher polyvalent carboxylic acid component include trimet acid, pyromet acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylene Carboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empol trimer acid, or anhydrides thereof, partial lower alkyl esters, and the like.

When the binder resin is a polyester-based resin, the molecular weight distribution of the THF-soluble component of the resin component has at least one peak in the molecular weight region of 3,000 to 50,000. In terms of THF, the THF-soluble component is preferably a binder resin in which a component having a molecular weight of 100,000 or less is 60 to 100%, and has at least one peak in the molecular weight region of 5,000 to 20,000. The binder resin present is more preferred.
When the binder resin is a polyester resin, the acid value thereof is preferably 0.1 mgKOH / g to 100 mgKOH / g, more preferably 0.1 mgKOH / g to 70 mgKOH / g, and 0.1 mgKOH / G to 50 mgKOH / g is most preferred.
In the present invention, the molecular weight distribution of the binder resin is measured by gel permeation chromatography (GPC) using THF as a solvent.

As the binder resin that can be used in the toner of the present invention, it is also possible to use a resin containing a monomer component capable of reacting with both of these resin components in at least one of the vinyl polymer component and the polyester resin component. it can. Examples of monomers that can react with the vinyl polymer among the monomers constituting the polyester resin component include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Examples of the monomer constituting the vinyl polymer component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.
Moreover, when using together a polyester polymer, a vinyl polymer, and another binder resin, what has 60 mass% or more of resin whose acid value of the whole binder resin has 0.1-50 mgKOH / g is preferable.
In the present invention, the acid value of the binder resin component of the toner composition is determined by the following method, and the basic operation conforms to JIS K-0070.
(1) The sample is used after removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the crosslinked binder resin are previously determined. I ask for it. The sample pulverized product 0.5 to 2.0 g is precisely weighed, and the weight of the polymer component is defined as Wg. For example, when the acid value of the binder resin is measured from toner, the acid value and content of the colorant or magnetic material are separately measured, and the acid value of the binder resin is obtained by calculation.
(2) A sample is put into a 300 ml beaker, and a mixed solution 150 (ml) of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(3) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / l KOH.
(4) The usage amount of the KOH solution at this time is set to Sml, and a blank is measured at the same time. The usage amount of the KOH solution at this time is set to Bml, and the following formula (1) is used. However, f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W (1)
The binder resin of the toner and the composition containing the binder resin preferably have a glass transition temperature (Tg) of 35 to 80 ° C., more preferably 40 to 75 ° C., from the viewpoint of toner storage stability. preferable. If the Tg is lower than 35 ° C., the toner is likely to deteriorate under a high temperature atmosphere, and offset may easily occur during fixing. On the other hand, when Tg exceeds 80 ° C., fixability may be deteriorated.

Examples of the magnetic material that can be used in the present invention include (1) iron oxide containing magnetic iron oxide such as magnetite, maghemite, and ferrite, and other metal oxides, (2) metals such as iron, cobalt, nickel, or Alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, (3) and these A mixture of
Specific examples of the magnetic material include Fe ₃ O ₄ , γ-Fe ₂ O ₃ , ZnFe ₂ O ₄ , Y ₃ Fe ₅ O ₁₂ , CdFe ₂ O ₄ , Gd ₃ Fe ₅ O ₁₂ , CuFe ₂ O _4. , PbFe ₁₂ O, NiFe ₂ O ₄ , NdFe ₂ O, BaFe ₁₂ O ₁₉ , MgFe ₂ O ₄ , MnFe ₂ O ₄ , LaFeO ₃ , iron powder, cobalt powder, nickel powder, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, fine powders of triiron tetroxide and γ-iron trioxide are particularly preferable.
Further, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements, or a mixture thereof can be used. Examples of different elements include, for example, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, And gallium. Preferred heterogeneous elements are selected from magnesium, aluminum, silicon, phosphorus, or zirconium. The foreign element may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as an oxide, or may be present on the surface as an oxide or hydroxide. Is preferably contained as an oxide.
The different elements can be incorporated into the particles by mixing the salts of the different elements at the time of producing the magnetic substance and adjusting the pH. Moreover, it can precipitate on the particle | grain surface by adjusting pH after the said magnetic body particle | grain production | generation, or adding the salt of each element and adjusting pH.
As the usage-amount of the said magnetic body, the said magnetic body is 10-200 mass parts with respect to 100 mass parts of said binder resins, and 20-150 mass parts is more preferable. The number average particle diameter of these magnetic materials is preferably 0.1 to 2 μm, and more preferably 0.1 to 0.5 μm. The number average diameter can be determined by measuring an enlarged photograph taken with a transmission electron microscope with a digitizer or the like.
As the magnetic properties of the magnetic material, those having a coercive force of 20 to 150 oersted, a saturation magnetization of 50 to 200 emu / g, and a residual magnetization of 2 to 20 emu / g are preferable.
The magnetic material can also be used as a colorant.

--Colorant--
The colorant is not particularly limited, and a commonly used resin can be appropriately selected and used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Fu Issey Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Nacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide , Pyridian, emerald green, pigment green B, naphthol green B, green gold, acid green , Malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof.
The content of the colorant is preferably 1 to 15% by mass and more preferably 3 to 10% by mass with respect to the toner.

The colorant used in the present invention can also be used as a master batch combined with a resin. As the binder resin kneaded with the master batch, in addition to the modified and unmodified polyester resins mentioned above, for example, polystyrene, poly-p-chlorostyrene, polyvinyltoluene and other styrene and its substituted polymers; styrene -P-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloro Methyl methacrylate copolymer, styrene-acrylic Ronitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene copolymers such as copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid Examples thereof include resins, rosins, modified rosins, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffin waxes. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.
The masterbatch can be obtained by mixing and kneading a resin for a masterbatch and a colorant with a high shearing force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. There is also a method for removing water and organic solvent components by mixing and kneading an aqueous paste containing water, which is a so-called flushing method, together with a resin and an organic solvent, and transferring the colorant to the resin side. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shearing dispersion device such as a three roll mill is preferably used.
The amount of the master batch used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

The resin for the masterbatch preferably has an acid value of 30 mgKOH / g or less, an amine value of 1 to 100, and a colorant dispersed therein. The acid value is 20 mgKOH / g or less and the amine value is 10 It is more preferable that the colorant is dispersed and used at ˜50. When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity may be lowered and the pigment dispersibility may be insufficient. Also, when the amine value is less than 1 and when the amine value exceeds 100, the pigment dispersibility may be insufficient. The acid value can be measured by the method described in JIS K0070, and the amine value can be measured by the method described in JIS K7237.
The dispersant is preferably highly compatible with the binder resin in terms of pigment dispersibility. Specific commercial products include “Ajisper PB821” and “Azisper PB822” (manufactured by Ajinomoto Fine Techno Co., Ltd.). ), “Disperbyk-2001” (manufactured by Big Chemie), “EFKA-4010” (manufactured by EFKA), and the like.
The dispersant is preferably blended in the toner at a ratio of 0.1 to 10% by mass with respect to the colorant. When the blending ratio is less than 0.1% by mass, the pigment dispersibility may be insufficient, and when it is more than 10% by mass, the chargeability under high humidity may be deteriorated.
The mass average molecular weight of the dispersant is the maximum molecular weight of the main peak in terms of styrene in gel permeation chromatography, and is preferably 500 to 100,000, and from the viewpoint of pigment dispersibility, 3,000 to 100 1,000 is more preferable. In particular, 5,000 to 50,000 are preferable, and 5,000 to 30,000 are most preferable. When the molecular weight is less than 500, the polarity increases and the dispersibility of the colorant may decrease. When the molecular weight exceeds 100,000, the affinity with the solvent increases and the dispersibility of the colorant decreases. There are things to do.
The addition amount of the dispersant is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the colorant. If it is less than 1 part by mass, the dispersibility may be lowered, and if it exceeds 50 parts by mass, the chargeability may be lowered.

-Other ingredients-
<Career>
The toner of the present invention may be mixed with a carrier and used as a two-component developer. As the carrier, ordinary carriers such as ferrite and magnetite and resin-coated carriers can be used.
The resin-coated carrier comprises a carrier core particle and a coating material that is a resin that coats (coats) the surface of the carrier core particle.
Examples of the resin used for the covering material include styrene-acrylic resins such as styrene-acrylic acid ester copolymers and styrene-methacrylic acid ester copolymers, acrylic acid ester copolymers, and methacrylic acid ester copolymers. Preferable examples include fluorine-containing resins such as acrylic resins, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, and polyvinylidene fluoride, silicone resins, polyester resins, polyamide resins, polyvinyl butyral, and aminoacrylate resins. In addition to these, resins that can be used as a coating (coating) material for carriers such as an ionomer resin and a polyphenylene sulfide resin can be used. These resins may be used alone or in combination of two or more.
Also, binder-type carrier core particles in which magnetic powder is dispersed in a resin can be used.
In the resin-coated carrier, as a method of coating the surface of the carrier core particles with at least a resin coating agent, the resin is dissolved or suspended in a solvent and adhered to the applied carrier core, or simply mixed in a powder state. The method is applicable.
The ratio of the resin coating material to the resin-coated carrier may be appropriately determined, but is preferably 0.01 to 5% by mass and more preferably 0.1 to 1% by mass with respect to the resin-coated carrier.
Examples of use in which a magnetic substance is coated with a coating agent of two or more kinds of mixtures include (1) dimethyldichlorosilane and dimethylsilicone oil (mass ratio 1: 5) with respect to 100 parts by mass of fine titanium oxide powder. Those treated with 12 parts by mass of the mixture, and (2) those treated with 20 parts by mass of a mixture of dimethyldichlorosilane and dimethylsilicone oil (mass ratio 1: 5) with respect to 100 parts by mass of the silica fine powder.

Among the resins, a styrene-methyl methacrylate copolymer, a mixture of a fluorine-containing resin and a styrene copolymer, and a silicone resin are preferably used, and a silicone resin is particularly preferable.
Examples of the mixture of the fluororesin and the styrene copolymer include, for example, a mixture of polyvinylidene fluoride and a styrene-methyl methacrylate copolymer, and a mixture of polytetrafluoroethylene and a styrene-methyl methacrylate copolymer. , Vinylidene fluoride-tetrafluoroethylene copolymer (copolymer mass ratio 10:90 to 90:10), styrene-acrylic acid 2-ethylhexyl copolymer (copolymer mass ratio 10:90 to 90:10) and styrene -A mixture with 2-ethylhexyl acrylate-methyl methacrylate copolymer (copolymer mass ratio 20-60: 5-30: 10: 50) is mentioned.
Examples of the silicone resin include modified silicone resins produced by reacting a nitrogen-containing silicone resin and a nitrogen-containing silane coupling agent with a silicone resin.
Examples of the magnetic material for the carrier core particles include oxides such as ferrite, iron-rich ferrite, magnetite, and γ-iron oxide, metals such as iron, cobalt, and nickel, or alloys thereof. .
Examples of elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, and vanadium. It is done. Of these, copper-zinc-iron-based ferrites mainly composed of copper, zinc, and iron components, and manganese-magnesium-iron-based ferrites mainly composed of manganese, magnesium, and iron components are preferable.

The resistance value of the carrier is preferably 10 ⁶ to 10 ¹⁰ Ω · cm by adjusting the degree of unevenness on the surface of the carrier and the amount of resin to be coated.
The carrier having a particle diameter of 4 to 200 μm can be used, preferably 10 to 150 μm, more preferably 20 to 100 μm. In particular, the resin-coated carrier preferably has a 50% particle size of 20 to 70 μm.
In the two-component developer, it is preferable to use 1 to 200 parts by mass of the toner of the present invention with respect to 100 parts by mass of the carrier, and 2 to 50 parts by mass of toner with respect to 100 parts by mass of the carrier. More preferred.

<Wax>
In the present invention, a wax can be contained together with the binder resin and the colorant.
The wax of the present invention is not particularly limited, and those that are usually used can be appropriately selected and used. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, sax. Plant waxes such as aliphatic hydrocarbon waxes such as sol wax, oxides of aliphatic hydrocarbon waxes such as polyethylene oxide wax or block copolymers thereof, candelilla wax, carnauba wax, wood wax, jojoba wax, etc. Waxes mainly composed of animal waxes such as beeswax, lanolin and spermaceti, mineral waxes such as ozokerite, ceresin and petrolatum, and fatty acid esters such as montanic ester wax and castor wax. Deoxidized carnauba wax and other fatty acid esters that have been partially or wholly deoxidized are included.
Examples of the wax further include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or linear alkyl carboxylic acids having a linear alkyl group, prandidic acid, eleostearic acid, and valinal acid. Unsaturated fatty acids such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnapyl alcohol, seryl alcohol, mesyl alcohol, or long-chain alkyl alcohols, polyhydric alcohols such as sorbitol, linoleic acid amides, olefinic acids Fatty acid amides such as amide and lauric acid amide, methylene biscapric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide and other saturated fatty acid bisamides, ethylene bis oleic acid amide, hexamethylene bis Unsaturated fatty acid amides such as oleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sepasinic acid amide, m-xylene bisstearic acid amide, N, N-distearyl isophthalic acid Grafted with aromatic bisamides such as amides, fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate, and aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid. Examples thereof include wax, a partial ester compound of a polyhydric alcohol such as a behenic acid monoglyceride, and a methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oil.
More preferred examples include polyolefins obtained by radical polymerization of olefins under high pressure, polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins, and polymerization using a catalyst such as a Ziegler catalyst or a metallocene catalyst under low pressure. Polyolefins, polyolefins polymerized using radiation, electromagnetic waves or light, low molecular weight polyolefins obtained by thermal decomposition of high molecular weight polyolefins, paraffin wax, microcrystalline wax, Fitzscher Tropsch wax, Jintole method, hydrocol method, age method Synthetic hydrocarbon waxes synthesized by the above, synthetic waxes having a compound having one carbon atom, hydrocarbon waxes having functional groups such as hydroxyl groups or carboxyl groups, hydrocarbon waxes and hydrocarbons having functional groups Mixture of system wax, styrene these waxes as a matrix, maleic acid ester, acrylate, methacrylate, graft-modified wax with such vinyl monomers of maleic acid.
In addition, these waxes have a sharp molecular weight distribution using a press perspiration method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, or a solution liquid crystal deposition method, a low molecular weight solid fatty acid, a low A molecular weight solid alcohol, a low molecular weight solid compound, and other impurities are preferably used.
The melting point of the wax is preferably 70 to 140 ° C., and more preferably 70 to 120 ° C., in order to balance the fixability and the offset resistance. If it is less than 70 degreeC, blocking resistance may fall, and if it exceeds 140 degreeC, an offset-proof effect may become difficult to express.

Further, by using two or more different types of waxes in combination, the plasticizing action and the releasing action which are the actions of the wax can be expressed simultaneously.
Examples of the types of wax having a plasticizing action include waxes having a low melting point, those having a branch on the molecular structure, and those having a polar group.
Examples of the wax having a releasing action include a wax having a high melting point, and the molecular structure includes a linear structure and a non-polar one having no functional group. Examples of use include a combination of two or more different waxes having a melting point difference of 10 ° C. to 100 ° C., a combination of polyolefin and graft-modified polyolefin, and the like.
When selecting two types of wax, in the case of a wax having a similar structure, a wax having a relatively low melting point exhibits a plasticizing action, and a wax having a high melting point exhibits a releasing action. At this time, when the difference in melting point is 10 to 100 ° C., functional separation is effectively expressed. If it is less than 10 ° C., the function separation effect may be difficult to appear, and if it exceeds 100 ° C., the function may not be emphasized by interaction. At this time, the melting point of at least one of the waxes is preferably 70 to 120 ° C, and more preferably 70 to 100 ° C, because the function separation effect tends to be easily exhibited.
As for the wax, those having a branched structure, those having a polar group such as a functional group, and those modified with a component different from the main component exert a plastic action, and those having a more linear structure or a functional group Nonpolar or non-denatured straight materials that do not have a mold exhibit a releasing action. Preferred combinations include polyethylene homopolymers or copolymers based on ethylene and polyolefin homopolymers or copolymers based on olefins other than ethylene, polyolefins and graft modified polyolefins, alcohol waxes, fatty acid waxes or ester waxes. And hydrocarbon wax combinations, Fischer-Tropsch wax or polyolefin wax and paraffin wax or microcrystal wax combination, Fischer-Tropsch wax and polyolefin wax combination, paraffin wax and microcrystal wax combination, Carnauba Wax, Can Delila wax, rice wax or montan wax and hydrocarbon-based wax Like a combination of.
In any case, since it becomes easy to balance the toner storage stability and the fixing property, the peak top temperature of the maximum peak may be in the region of 70 to 110 ° C. in the endothermic peak observed in the DSC measurement of the toner. Preferably, it has a maximum peak in the region of 70 to 110 ° C.
The total content of the wax is preferably 0.2 to 20 parts by mass and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin.
In the present invention, the peak top temperature of the endothermic peak of the wax measured by DSC is defined as the melting point of the wax.
The wax or toner DSC measuring device is preferably measured with a high-precision internal heat input compensation type differential scanning calorimeter. As a measuring method, it carries out according to ASTM D3418-82. The DSC curve used in the present invention is one that is measured when the temperature is raised at a temperature rate of 10 ° C./min after once raising and lowering the temperature and taking a previous history.

<Fluidity improver>
A fluidity improver may be added to the toner of the present invention. The fluidity improver improves the fluidity of the toner (becomes easy to flow) when added to the toner surface.
Examples of the fluidity improver include, for example, carbon black, vinylidene fluoride fine powder, fluorine-based resin powder such as polytetrafluoroethylene fine powder, wet process silica, fine powder silica such as dry process silica, fine powder unoxidized titanium, Examples include finely powdered non-alumina, treated silica obtained by subjecting them to a surface treatment with a silane coupling agent, a titanium coupling agent or silicone oil, treated titanium oxide, and treated alumina. Among these, fine powder silica, fine powder non-titanium oxide, and fine powder non-alumina are preferable, and treated silica obtained by performing surface treatment with a silane coupling agent or silicone oil is more preferable.
The particle size of the fluidity improver is preferably 0.001 to 2 μm, more preferably 0.002 to 0.2 μm, as an average primary particle size.
The fine powder silica is a fine powder produced by vapor phase oxidation of a silicon halide inclusion, and is called so-called dry silica or fumed silica.
Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include AEROSIL (trade name of Nippon Aerosil Co., Ltd., hereinafter the same) -130, -300, -380, -TT600, -MOX170, -MOX80, -COK84: Ca-O-SiL (trade name of CABOT) -M-5, -MS-7, -MS-75, -HS-5, -EH-5, Wacker HDK (trade name of WACKER-CHEMIEGMBH)- N20 V15, -N20E, -T30, -T40: D-CFineSi1ica (trade name of Dow Corning): Franco1 (trade name of Franci1), and the like.
Furthermore, a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of a silicon halogen compound is more preferable. In the treated silica fine powder, it is particularly preferred to treat the silica fine powder so that the degree of hydrophobicity measured by a methanol titration test is preferably 30 to 80%. Hydrophobization is imparted by chemical or physical treatment with an organosilicon compound that reacts or physically adsorbs with silica fine powder. As a preferred method, a method of treating a silica fine powder produced by vapor phase oxidation of a silicon halogen compound with an organosilicon compound is preferable.
Examples of the organosilicon compound include hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, vinylmethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and dimethylvinylchlorosilane. , Divinylchlorosilane, γ-methacryloxypropyltrimethoxysilane, hexamethyldisilane, trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-Chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchloro Silane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane , Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 2 to 12 siloxane units per molecule, Examples include dimethylpolysiloxane containing 0 to 1 hydroxyl group bonded to Si. Furthermore, silicone oils such as dimethyl silicone oil can be mentioned. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.
The number average particle diameter of the fluidity improver is preferably 5 to 100 nm, more preferably 5 to 50 nm.
The specific surface area by measuring nitrogen adsorption by the BET method, preferably at least ^{30m 2 / g, 60~400m 2 /} g is more preferable.
The surface-treated fine powder, preferably at least ^{20m 2 / g, 40~300m 2 /} g is more preferable.
The application amount of these fluidity improvers is preferably 0.03 to 8 parts by mass with respect to 100 parts by mass of the toner particles.

In the toner of the present invention, as other additives, protection of the electrostatic latent image carrier / carrier, improvement of cleaning properties, adjustment of thermal characteristics / electrical characteristics / physical characteristics, resistance adjustment, adjustment of softening point, improvement of fixing rate For purposes such as various types of metal soaps, fluorine surfactants, dioctyl phthalate, tin oxide, zinc oxide, carbon black, antimony oxide, etc. as conductivity imparting agents, inorganic fine powders such as titanium oxide, aluminum oxide, alumina, etc. A body etc. can be added as needed. These inorganic fine powders may be hydrophobized as necessary. Also, lubricants such as polytetrafluoroethylene, zinc stearate, and polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, and strontium titanate, anti-caking agents, and white and black fine particles having opposite polarity to the toner particles Can also be used in small amounts as a developability improver.
These additives include silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicon compounds for the purpose of charge control and the like. It is also preferable to treat with a treating agent or various treating agents.
When preparing the developer, inorganic fine particles such as the hydrophobic silica fine powder mentioned above may be added and mixed in order to improve the fluidity, storage stability, developability and transferability of the developer. For mixing external additives, a general powder mixer can be appropriately selected and used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually, or the rotational speed, rolling speed, time, temperature, etc. of the mixer may be changed. The load may then be given a relatively weak load and vice versa.
Examples of the mixer that can be used include a V-type mixer, a rocking mixer, a Roedige mixer, a Nauter mixer, a Henschel mixer, and the like.
A method for further adjusting the shape of the obtained toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a toner material composed of a binder resin and a colorant is melt-kneaded and then finely pulverized. Using a hybridizer, mechano-fusion, etc., and adjusting the shape mechanically, or so-called spray-drying method, the toner material is dissolved and dispersed in a solvent in which the toner binder is soluble, and then spray-dried. Examples thereof include a method of removing a solvent to obtain a spherical toner and a method of forming a spherical toner by heating in an aqueous medium.

As the external additive, inorganic fine particles can be preferably used.
Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, and diatomaceous earth. , Chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, and the like.
The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and more preferably 5 mμ to 500 mμ.
The specific surface area according to the BET method is preferably 20 to 500 m ² / g.
The proportion of the inorganic fine particles used is preferably 0.01 to 5% by mass of the toner, and more preferably 0.01 to 2.0% by mass.
In addition, polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine and nylon, thermosetting resin And polymer particles.
Such an external additive can be made hydrophobic by the surface treatment agent and prevent deterioration of the external additive itself even under high humidity.
Examples of the surface treatment agent include a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, a modified silicone oil, Etc. are preferable.
The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and more preferably 5 mμ to 500 mμ. Moreover, as a specific surface area by BET method, it is preferable that it is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by mass of the toner, and more preferably 0.01 to 2.0% by mass.

  Examples of the cleaning property improver for removing the developer after transfer remaining on the electrostatic latent image carrier or the primary transfer medium include fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, and polymethyl methacrylate. There may be mentioned polymer fine particles produced by soap-free emulsion polymerization such as fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

  In the developing method of the present invention, all of the electrostatic latent image carriers used in the conventional electrophotographic methods can be used. For example, an organic electrostatic latent image carrier, an amorphous silica electrostatic latent image carrier, and a selenium static image carrier. An electrostatic latent image carrier, a zinc oxide electrostatic latent image carrier, and the like can be suitably used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example at all.

Example 1
-Preparation of colorant dispersion-
First, a carbon black dispersion as a colorant was prepared.
Carbon black (Regal 400; manufactured by Cabot) (15 parts by mass) and a pigment dispersant (3 parts by mass) were primarily dispersed in 82 parts by mass of ethyl acetate using a mixer having stirring blades. As the pigment dispersant, Ajisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) was used. The obtained primary dispersion was finely dispersed by a strong shearing force using a dyno mill to prepare a rainbow dispersion in which aggregates were completely removed. Furthermore, a liquid having a pore size of 0.45 μm (manufactured by PTFE) and passing through a submicron region was prepared.

-Preparation of dispersion with added resin and wax-
Next, a dispersion liquid having the following composition to which a resin as a binder resin and a wax were added was prepared.
100 parts by weight of polyester resin as a binder resin, 30 parts by weight of the carbon black dispersion, 5 parts by weight of carnauba wax, 1,000 parts by weight of ethyl acetate, and a mixer having stirring blades as in the preparation of the colorant dispersion And stirred for 10 minutes to disperse. It was possible to completely prevent pigments from aggregating due to shock caused by solvent dilution. The dispersion at this stage was filtered through a 0.45 μm filter (made by PTFE) in the same manner as in the preparation of the colorant dispersion, but it was confirmed that no clogging occurred and all passed. The electrolytic conductivity of this dispersion was 3.5 × 10 ⁻⁷ S / m.

-Preparation of toner-
The obtained dispersion was supplied to the nozzle 1 of the toner production apparatus shown in FIGS. The nozzle used was a nickel plate having a thickness of 20 μm, and a perfectly circular discharge hole having a diameter of 10 μm was produced by processing with a femtosecond laser.
After the dispersion liquid was prepared, the liquid droplets were discharged under the following toner production conditions, and then the liquid droplets were dried and solidified to produce a toner.
[Toner preparation conditions]
Dispersion specific gravity: ρ = 1.888 g / cm ³
Dry air flow rate: Orifice sheath 2.0 L / min, In-apparatus air 3.0 L / min Dry air temperature: 80-82 ° C.
In-apparatus temperature: 27-28 ° C
Dew point temperature: -20 ° C
Electrode applied voltage: 2.5 KV
Nozzle frequency: 220 kHz
The dried and solidified toner particles were collected by suction with a filter having 1 μm pores. Particle size of collected particles The particle size distribution of the collected particles was measured with a flow type particle image analyzer (FPIA-2000). The mass average particle size was 6.0 μm, and the number average particle size was 6.0 μm. Toner base particles that were completely monodispersed were obtained. A scanning electron micrograph of this toner base is shown in FIG.

-Toner evaluation-
The obtained toner was evaluated as follows. The results are shown in Table 1.
<Particle size distribution>
The mass average particle diameter (D4) and the number average particle diameter (Dn) of the toner of the present invention are measured with an aperture diameter of 100 μm using a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.), and analysis software ( Beckman Coulter Multisizer
3 Version 3.51).
Specifically, 0.5 ml of 10% by weight surfactant (alkylbenzene sulfonate Neogen SC-A, Daiichi Kogyo Seiyaku) is added to a glass 100 ml beaker, and 0.5 g of each toner is added to make microscopic. The mixture was stirred with a spatula, and then 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured with the Multisizer III using Isoton III (manufactured by Beckman Coulter) as a measurement solution. The measurement was performed by dropping the toner sample dispersion so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of measurement reproducibility of the particle diameter. Within this concentration range, no error occurs in the particle size. As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 .35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to less than 12.70 μm; 12.70 to less than 16.00 μm; 16.00 to less than 20.20 μm; Particles with a particle size of 2.00 μm to less than 40.30 μm were used using 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm.
After measuring the volume and number of toner particles or toner, the volume distribution and number distribution were calculated. From the obtained distribution, the mass average particle diameter (D4) and the number average particle diameter (Dn) of the toner can be obtained. As an index of the particle size distribution, D4 / Dn obtained by dividing the toner mass average diameter (D4) by the number average particle diameter (Dn) was used. If it is completely monodisperse, it becomes 1, and the larger the value, the wider the distribution.

<Charge amount>
It was measured with a suction type charge amount measuring device. Specifically, the toner was sucked in a range of 200 to 250 mg in a Faraday cage equipped with a filter capable of collecting the toner, and an electrometer was connected thereto, and the total charge amount of the sucked toner was measured. At this time, the mass increased from the previously measured filter mass is measured with a five-digit precision chemical balance as the toner mass on the filter, the total charge is divided by the collected toner mass, and the charge per unit mass (q / M). There is “Model 210HS-2A” manufactured by Trek Japan Co., Ltd. as a commercially available charge amount measuring device having the same measurement principle, but a self-made measuring device having the same configuration was used. A glass microfiber (Whatman) having a diameter of 21 mm was used as a filter for collecting the toner. Although there is almost no difference in measurement depending on the suction time, the suction time is specified within 30 seconds here.

<Amount of charge at room temperature and high humidity (NH)>
Measurement was carried out by the above-described charge amount measurement method in an environmental test room at a temperature of 30 ° C. and a humidity of 90%. The measurement was performed after leaving the sample in this environment for 12 hours.

<Charge amount distribution>
The charge amount distribution of the toner was measured by a charge amount distribution measuring device (E-Spart Analyzer EST-2 type manufactured by Hosokawa Micron Corporation). Specifically, the toner was directly introduced into the toner inlet of the measuring machine so that 500 to 600 particles could be measured per minute with a feeder, and the charge amount distribution was measured. The index indicating the distribution of the charge amount is represented by the mode (peak value) [q / d] and the distribution width (half width) at the half height position of the most frequent. As for the characteristics of the toner, it is preferable that the charge amount is high and the charge amount distribution is sharper, but generally, the half value width indicating the charge amount distribution tends to increase as the charge amount increases. If the mode value is 0.25 fC / μm or more and the half value width of the charge amount distribution is 0.2 or less, it is determined that the charge amount distribution is excellent.

<Thin wire reproducibility>
The developer was put into a modified machine in which a developing unit portion of a commercially available copying machine (Imagiono 271; manufactured by Ricoh) was improved, and running was performed using 6000 paper manufactured by Ricoh with a printing ratio of 7%. Compare the original 10th image and the 30,000th image thin line with the original, and observe it with an optical microscope at a magnification of 100x, and evaluate it in 4 stages while comparing the line missing state with the stage sample. did. The image quality is higher in the order of ◎>○>△> ×. In particular, the evaluation of x is a level that cannot be adopted as a product. In the case of negatively charged toner, an organic electrostatic latent image carrier was used, and in the case of positively charged toner, an amorphous silicon electrostatic latent image carrier was used.
In development method 1, the toner was directly conveyed to the development site by an air stream and developed with a powder cloud. In development method 2, a resin-coated carrier used in conventional electrophotography was used as a conveying means. The following were used as carriers.
[Carrier]
Core material: Spherical ferrite particles with an average particle size of 50 μm Coating material constituent material: Silicone resin Disperse the silicone resin in toluene, adjust the dispersion, spray coat the core material in a heated state, fire, and cool, Carrier particles having an average coated resin film thickness of 0.2 μm were prepared.

(Example 2)
In Example 1, the target toner was obtained in the same manner as in Example 1 except that the diameter of the discharge hole was 5 μm and the solid content concentration was 8 times. Also in this case, the toner had a mass average particle diameter of 6.0 μm and a number average particle diameter of 6.0 μm, and completely monodispersed toner base particles were obtained.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

(Example 3)
In Example 1, the target toner was obtained in the same manner as in Example 1 except that the diameter of the ejection hole was 20 μm and the solid content concentration was 0.125 times. Also in this case, the toner had a mass average particle diameter of 6.0 μm and a number average particle diameter of 6.0 μm, and completely monodispersed toner base particles were obtained.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

Example 4
In Example 1, the target toner was obtained in the same manner as in Example 1 except that the nozzle frequency was 440 kHz and the liquid flow rate supplied from the syringe pump was doubled. Also in this case, the toner had a mass average particle diameter of 6.0 μm and a number average particle diameter of 6.0 μm, and completely monodispersed toner base particles were obtained.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

(Example 5)
In Example 1, the target toner was obtained in the same manner as in Example 1 except that the nozzle frequency was 110 kHz and the liquid flow rate supplied from the syringe pump was 0.5 times. Also in this case, the toner had a mass average particle diameter of 6.0 μm and a number average particle diameter of 6.0 μm, and completely monodispersed toner base particles were obtained.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

(Example 6)
A target toner was obtained in the same manner as in Example 1 except that in Example 1, a styrene acrylic copolymer resin having a specific gravity of 1.05 was used instead of the polyester resin. Also in this case, the toner had a mass average particle diameter of 6.0 μm and a number average particle diameter of 6.0 μm, and thus completely monodispersed toner base particles were obtained. To be different from the results of Example 1. A scanning electron micrograph of this toner base is shown in FIG.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

(Example 7)
Instead of the nozzles used in Example 1, 10 nozzles with a perfect circle diameter of 10 μm were fabricated on a nickel plate with a thickness of 20 μm by processing with a femtosecond laser, and the center diameter of the plate was within a circle of 1.5 mm. A target toner was obtained in the same manner as in Example 1 except that 20 nozzles were provided concentrically and a total of 200 ejection holes were provided. Also in this case, the toner had a mass average particle diameter of 6.0 μm and a number average particle diameter of 6.0 μm, and completely monodispersed toner base particles were obtained.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

(Example 8)
In Example 1, the target toner was obtained in the same manner as in Example 1 except that the amount of ethyl acetate used in the dispersion added with resin and wax was changed to 5,350 parts by mass. Also in this case, the toner had a mass average particle diameter of 5.0 μm and a number average particle diameter of 5.0 μm, and completely monodispersed toner base particles were obtained. A scanning electron micrograph of this toner base is shown in FIG.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

Example 9
In Example 1, the target toner was obtained in the same manner as in Example 1 except that the amount of ethyl acetate used in the dispersion added with resin and wax was 10,449 parts by mass. Also in this case, the toner had a mass average particle diameter of 4.0 μm and a number average particle diameter of 4.0 μm, and completely monodispersed toner base particles were obtained. A scanning electron micrograph of this toner base is shown in FIG.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

(Example 10)
In Example 1, the target toner was obtained in the same manner as in Example 1 except that the amount of ethyl acetate used in the dispersion added with resin and wax was 24,767 parts by mass. Also in this case, the toner had a mass average particle diameter of 3.0 μm and a number average particle diameter of 3.0 μm, and completely monodispersed toner base particles were obtained. A scanning electron micrograph of this toner base is shown in FIG.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

(Comparative Example 1)
-Preparation of dispersion-
A colorant dispersion, a dispersion containing a resin and a wax were prepared under the same conditions as in Example 1.

-Preparation of toner-
In place of the apparatus used in Example 1, a storage unit for storing the dispersion liquid and a head unit capable of applying a piezoelectric pulse to the storage unit by expansion and contraction of a piezoelectric body and discharging droplets from the nozzles are provided. Then, after the droplets were discharged under the following toner production conditions, the toner was produced by drying and solidifying the droplets. The apparatus of Example 1 has a structure in which vibration is applied to the nozzle itself, whereas the apparatus of Comparative Example 1 is greatly different in that a piezoelectric pulse is applied to the dispersion liquid storage unit.
[Toner preparation conditions]
Dispersion specific gravity: ρ = 1.888 g / cm ³
Dry air flow rate: Air in the apparatus 3.0 L / min Dry air temperature: 80-82 ° C
In-apparatus temperature: 27-28 ° C
Dry air (dew point temperature): -20 ° C
Piezoelectric pulse frequency: 20 kHz
The dried and solidified toner particles were collected by suction with a filter having 1 μm pores. Particle size of collected particles The particle size distribution of the collected particles was measured with a flow type particle image analyzer (FPIA-2000). The mass average particle size was 7.8 μm, and the number average particle size was 5.2 μm. Toner base particles having a wide particle size distribution were obtained. A scanning electron micrograph of this toner base is shown in FIG.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

(Comparative Example 2)
-Preparation of dispersion-
A colorant dispersion, a dispersion containing a resin and a wax were prepared under the same conditions as in Example 1.

-Preparation of toner-
In place of the apparatus used in Example 1, a storage unit for storing a dispersion liquid, and a piezoelectric pulse generated by the expansion and contraction of a piezoelectric body in the storage unit, and a pressure pulse obtained by converging with an acoustic lens, a droplet The toner was produced under the same conditions as in Comparative Example 1 except that the apparatus was provided with a head unit capable of ejecting from the nozzle. The apparatus of Example 1 has a structure in which vibration is applied to the nozzle itself, whereas the apparatus of Comparative Example 2 is greatly different in that a piezoelectric pulse is applied to the dispersion liquid storage unit.
The dried and solidified toner particles were collected by suction with a filter having 1 μm pores. Particle size of the collected particles The particle size distribution of the collected particles was measured with a flow particle image analyzer (FPIA-2000). The mass average particle size was 7.2 μm, and the number average particle size was 5.6 μm. Toner base particles having a wide particle size distribution were obtained. A scanning electron micrograph of this toner base is shown in FIG.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

(Comparative Example 3)
-Preparation of dispersion-
A colorant dispersion, a dispersion containing a resin and a wax were prepared under the same conditions as in Example 1.

Instead of the droplet discharge unit of the apparatus used in Example 1, heat energy is given by a storage unit that stores the dispersion, and a heating element that generates heat by applying an alternating voltage to the dispersion stored in the storage unit, Toner was produced under the same conditions as in Comparative Example 1 instead of the apparatus provided with a head part capable of ejecting droplets from the nozzle by volume expansion due to bubbles in the storage part generated at this time.
The dried and solidified toner particles were collected by suction with a filter having 1 μm pores. Particle size of collected particles The particle size distribution of the collected particles was measured with a flow type particle image analyzer (FPIA-2000). The mass average particle size was 7.9 μm, and the number average particle size was 4.6 μm. Toner base particles having a large particle size distribution with many fine particles of 1 μm or less were obtained. A scanning electron micrograph of this toner base is shown in FIG.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

As shown in Table 1, it was found that the toner can be efficiently converted into a toner according to the present invention, and the toner characteristics are extremely good. In addition, an image obtained by developing using the toner produced in the present invention was extremely excellent in image quality faithful to the electrostatic latent image.

  The toner production method and toner production apparatus of the present invention can produce toner efficiently and, furthermore, are particles having a monodispersibility with an unprecedented particle size. In many of the characteristic values required for toner, there is no or very little variation due to particles as seen in conventional manufacturing methods, so electrostatic charge in electrophotography, electrostatic recording, electrostatic printing, etc. It is suitably used as a developer for developing an image.

FIG. 1 is a schematic view of an apparatus (toner manufacturing apparatus) including a nozzle. FIG. 2 is an enlarged schematic view of the nozzle portion of the toner manufacturing apparatus. FIG. 3 is a scanning electron micrograph of the toner base produced in Example 1. FIG. 4 is a scanning electron micrograph of the toner base produced in Example 6. FIG. 5 is a scanning electron micrograph of the toner base produced in Example 8. FIG. 6 is a scanning electron micrograph of the toner base produced in Example 9. FIG. 7 is a scanning electron micrograph of the toner base produced in Example 10. FIG. 8 is a scanning electron micrograph of the toner base produced in Comparative Example 1. FIG. 9 is a scanning electron micrograph of the toner base produced in Comparative Example 2. FIG. 10 is a scanning electron micrograph of the toner base produced in Comparative Example 3.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Nozzle 2 Electrode 3 Solvent removal equipment 4 Electric discharger 5 Toner collection part 6 Toner particle (toner)
DESCRIPTION OF SYMBOLS 7 Eddy current 8 Electric field curtain 9 Liquid conveyance tube 10 Drying container 11 Droplet 12 Toner storage container 13 Drying gas supply tube 14 Metering pump 15 Slurry dispersion liquid reservoir 16 Insulating substrate 17 Liquid supply apparatus 18 DC high voltage power supply 19 O ring 20 Dispersion Air 21 Piezoelectric body

Claims (32)

  A toner composition fluid containing a toner composition containing at least a resin and a colorant is ejected from a nozzle oscillated at a constant frequency to form droplets, which are solidified into particles. Toner manufacturing method.   A toner manufacturing method comprising: discharging or dissolving a solution or dispersion of a toner material containing at least a resin and a colorant from a nozzle oscillated at a constant frequency to form droplets; .   The toner manufacturing method according to claim 1, further comprising vibration generating means for vibrating the nozzle.   The toner manufacturing method according to claim 3, wherein the vibration generating unit and the nozzle are in contact with each other, and the nozzle is directly vibrated by the vibration generating unit.   The toner manufacturing method according to claim 3, wherein the vibration generating means is a piezoelectric body and is vibrated at a constant frequency by expansion and contraction of the piezoelectric body.   The toner manufacturing method according to claim 1, wherein the nozzle discharge hole is formed of a metal plate having a thickness of 5 to 50 μm, and the opening diameter thereof is 3 to 35 μm.   The toner manufacturing method according to claim 1, wherein a positive charge or a negative charge is given to the liquid droplets ejected from the nozzle by induction charging.   The toner manufacturing method according to claim 7, wherein the induction charging is performed by passing a droplet discharged from a nozzle between a pair of electrodes to which a DC voltage is applied. The method for producing a toner according to any one of claims 2 to 8, wherein the electrolytic conductivity of the solution or dispersion of the toner material containing at least a resin and a colorant is 1.0 × 10 ^-7 S / m or more. . 10. The electrolytic conductivity as a solvent of a solution or dispersion of a toner material containing at least a resin and a colorant is 1.0 × 10 ⁻⁷ S / m or more. Toner manufacturing method.   By causing a dry gas to flow in the same direction as the droplet discharge direction, an air flow is generated, and the air flow causes the droplets to be transported in the solvent removal equipment, and the solvent in the droplets is removed during the transport. The toner manufacturing method according to claim 1, wherein toner particles are formed.   The toner manufacturing method according to claim 11, wherein the dry gas is one of air and nitrogen gas.   The method for producing a toner according to claim 11, wherein the temperature of the dry gas is 40 to 200 ° C.   14. The solvent removal apparatus has a transport path whose periphery is covered with an electrostatic curtain charged to a polarity opposite to the charge of the droplet, and allows the droplet to pass through the transport path. The toner manufacturing method in any one.   A toner manufactured by the toner manufacturing method according to claim 1.   The toner according to claim 15, wherein the particle size distribution (mass average particle diameter / number average particle diameter) is in the range of 1.00 to 1.05.   The toner according to claim 16, having a mass average particle diameter of 1 to 20 μm.   A droplet forming means for forming a droplet by discharging a solution or dispersion of a toner material containing at least a resin and a colorant from a nozzle oscillated at a constant frequency, and included in the droplet And a toner particle forming unit that forms toner particles by drying the droplets by removing the solvent.   The toner manufacturing apparatus according to claim 18, wherein the droplet forming unit includes a vibration generating unit that directly vibrates the nozzle.   The toner manufacturing apparatus according to claim 19, wherein the vibration generating means vibrates the nozzle simultaneously with the passage of the dissolved or dispersed liquid.   21. The toner manufacturing apparatus according to claim 18, further comprising a storage unit that stores the dissolved or dispersed liquid of the toner material and supplies the dissolved or dispersed liquid of the toner material to the droplet forming unit.   The toner manufacturing apparatus according to any one of claims 18 to 21, wherein the nozzle is vibrated at a constant frequency by expansion and contraction of the piezoelectric body, and the number of ejection holes of the nozzle vibrated by the one piezoelectric body is 1 to 300. .   The toner manufacturing apparatus according to any one of claims 18 to 22, wherein a plurality of nozzles are provided, and droplets discharged from each nozzle are dried by a single solvent removal facility.   24. The toner manufacturing apparatus according to claim 18, wherein the constant frequency is 50 kHz to 50 MHz.   25. The toner manufacturing apparatus according to claim 18, wherein the constant frequency is 100 kHz to 10 MHz.   26. Any one of claims 18 to 25, wherein the charge of the toner particles formed by passing the droplets into the transport path is temporarily neutralized by a static eliminator, and then the toner particles are accommodated in the toner collecting portion. The toner manufacturing apparatus according to claim 1.   27. The toner manufacturing apparatus according to claim 26, wherein the static elimination by the static eliminator is performed by soft X-ray irradiation.   27. The toner manufacturing apparatus according to claim 26, wherein the charge removal by the charge eliminator is performed by plasma irradiation.   The toner collecting portion for collecting the toner particles has a tapered surface whose opening diameter is gradually reduced. From the outlet portion where the opening diameter is reduced from the inlet portion, the toner particles are dried using the dry gas. 29. The toner manufacturing apparatus according to claim 18, wherein a gas flow is formed and toner particles are transferred to the toner storage container by the dry gas flow.   30. The toner manufacturing apparatus according to claim 29, wherein the flow of the dry gas is a vortex.   31. The toner manufacturing apparatus according to claim 18, wherein the toner collecting unit and the toner storage container are formed of a conductive material, and are connected to the ground. 32. The toner manufacturing apparatus according to claim 18, wherein the toner manufacturing apparatus has an exposure prevention specification.